1. Field of the Invention
The invention relates to bridged perinones, quinophthalones and perinone-quinophthalones, processes for their preparation and their use for mass coloration of plastics.
2. Brief Description of the Prior Art
It is known to use perinone dyes as described for example in FR-A-1 075 110 or U.S. Pat. No. 5,466,805 for mass coloration of plastics. It is also known to use quinophthalone dyes as described for example in DE-A-44 35 714 or DE-A-21 32 681 for mass coloration of plastics. Compounds of this type are notable for good thermal stability and high light fastness, but their sublimation fastness is still in need of improvement. Illustratively, temperatures of above 240xc2x0 C. which occur in the coloration process in the injection moulding machines, lead all too commonly to an undesirable sublimation of the dye, contaminating the working equipment and necessitating costly and inconvenient cleaning measures. EP-A-827 986 already discloses doubled quinophthalone and perinone dyes possessing good sublimation fastness.
It is an object of the present invention to provide further sublimation-fast dyes for the mass coloration of plastic, which are preferably readily soluble in the monomeric starting materials of the plastic too in order that greater flexibility in the coloration of plastics may be ensured.
There have now been found compounds of the general formula (I) or tautomeric forms thereof 
where
Ar1 and Ar2 are independently radicals needed to complete optionally substituted carbocyclic aromatics,
B is a radical of the formula -T1-W-T2-, where
T1 and T2 are independently O or S and
W is alkylene, especially C1-C6-alkylene, C6-C10-arylene, especially phenylene or cycloalkylene, which are each optionally substituted or is the radical of the formula (a) 
xe2x80x83where the phenyl rings are optionally substituted and
A is a radical of the formula O, S, SO, SO2 or CO, optionally substituted alkylene, or optionally substituted cycloalkylene, said alkylene or cycloalkylene being attached to the adjacent phenyl rings itself or else via its substituents, or
W is a radical of the formulae 
xe2x80x83where
s and t are independently from 1 to 6,
the ends of the radical B each being attached to an aromatic carbon atom of the two radicals Ar1 and Ar2,
and
X1 and X2 are independently a radical of the formulae selected from the group consisting of 
each being located in the ring in such a way that the 
is adjacent to the Cxe2x80x94C double bond,
where
Y is a radical of an optionally substituted benzene or naphthalene ring,
Z is optionally substituted ortho-phenylene, ortho-naphthylene, peri-(1,8)-naphthylene or arylene composed of more than two fused-together benzene rings, aryl radicals which have more than two fused-together benzene rings being bridged ortho or in a manner corresponding to a peri position in naphthalene,
Ra is H or OH, and
Rb is H or halogen, especially F, Br or Cl.
The peri position actually denotes the 1,8-position in naphthalene. Both in the literature and in the context of the present application, however, this meaning is extended to include arylenes composed of more than two fused-together benzene rings.
Possible substituents for Z and for the two phenyl rings of the radical of the formula (a) include for example: C1-C6-alkyl, halogen, nitro, aryl, aryloxysulphonyl, hydroxyl, C1-C6-alkoxy, aryloxy, optionally alkyl- or acyl-substituted amino, optionally alkyl- or aryl-substituted aminosulphonyl, optionally alkyl-substituted carboxamide or a fused-on aromatic, cycloaliphatic or heterocyclic ring.
Preferred substituents are: chlorine, bromine, nitro, methoxy, NH2, benzyloxy, hydroxyl, xe2x80x94SO2O(C6H5), xe2x80x94SO2N(CH3)2, xe2x80x94SO2NHCH3, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, NHCOCH3, xe2x80x94N(C2H5)2 or optionally substituted phenyl.
Possible substituents for the benzene or naphthalene radical completed by Y include for example: halogen, especially Cl and Br, xe2x80x94COOH, xe2x80x94COOR, where R is C1-C10alkyl, preferably C1-C4-alkyl, especially methyl or ethyl, C6-C10-aryl or C5-C8-cycloalkyl, and C1-C6-alkyl, especially methyl.
Possible substituents for the carbocyclic aromatic completed by Ar1 and Ar2 include for example: C1-C6-alkyl, especially methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl and tert-butyl, halogen, especially Cl or Br, alkylcarbonyl, arylcarbonyl, alkylsulphonyl, arylsulphonyl, nitro, aryl, especially optionally substituted phenyl, aryloxysulphonyl, especially xe2x80x94SO2OC6H5, hydroxyl, C1-C6-alkoxy, such as methoxy or benzyloxy, aryloxy, such as phenoxy, optionally alkyl- or acyl-substituted amino such as NH2, NHCOCH3 or xe2x80x94N(C2H5)2, optionally alkyl- or aryl-substituted aminosulphonyl such as SO2N(CH3)2 or SO2NHCH3 or a fused-on aromatic, cycloaliphatic or heterocyclic ring.
Particularly preferably Ar1 and Ar2 are independently a radical needed to complete an optionally substituted benzene or naphthalene ring, especially an optionally substituted benzene ring.
Possible substituents for the alkylene group in W and A, which can be not only straight-chain but also branched, include for example halogen such as F or Cl, CF3, O, S, optionally substituted phenyl and C1-C6-alkyl.
Possible substituents for the cycloalkyl group, especially the C5-C6-cycloalkylene group, particularly preferably the cyclohexylidene group, include for example one or more C1-C4-alkyl radicals.
Particular preference is given to compounds of the formula (I) which conform to the formula (II) or tautomeric forms thereof 
where
Y1 and Y2 are independently the radical of an optionally substituted benzene or naphthalene ring,
Ra1 and Ra2 are independently H or OH, and
Rb1 and Rb2 are independently H or halogen, especially Br or Cl and
Ar1, Ar2 and B are each as defined above.
Possible substituents for the radicals Y1 and Y2 are for example the substituents indicated for the radical Y.
Particularly preferably Rb1 and Rb2 are each hydrogen.
Particular preference is given to compounds of the formula (II) which conform to the formula (IIa) or tautomeric forms thereof 
where
n and m are independently from 0 to 4,
R1 and R2 each independently have the same or different meanings as indicated for the substituents for the radicals completed by Y1 and Y2,
o and p are independently from 0 to 2, especially 0 or 1,
R3 and R4 each independently have the same or different meanings as indicated for the substituents for the carbocyclic aromatics completed by Ar1 and Ar2,
Rb1 and Rb2 are each as defined above and are preferably H,
Ra1 and Ra2 are each as defined above and are preferably OH, and
B is as defined above. The preferred B include 
xe2x80x83and also the corresponding dithio compounds (T1 and T2=S).
Also, the preferred B are those wherein W or A have the following meanings:
xe2x80x94CH2xe2x80x94, xe2x80x94CH2xe2x80x94CH2xe2x80x94, xe2x80x94CH2CH2CH2xe2x80x94, xe2x80x94CH2CH2CH2CH2xe2x80x94, 
Very particular preference is given to compounds of the formula (II) where
Y1=Y2 
Ra1=Ra2 
Rb1=Rb2 and
Ar1=Ar2.
Preference is also given to compounds of the formula (IIa) where
n=m,
R1=R2,
Ra1=Ra2,
Rb1=Rb2,
o=p and
R3=R4,
where in particular
n, m, o and p are each 0.
Particular preference is given to compounds of the formula (II) which conform to the formula (IIb) or tautomeric forms thereof 
where
n, m, R1, R2, Rb1, Rb2 and B are each as defined above.
The compounds of the formula (I) according to the invention are notable for excellent sublimation fastness in the mass coloration of plastics. They also possess very good light fastness, good thermal stability and particularly high colour strength. A colour strength comparison of for example the compounds of formula (II) with the non-doubled quinophthalones shows a disproportionately large increase (based on molecular weight increase).
When the quinophthalones of the formula (II) according to the invention have different meanings for Y1 and Y2 and/or Ra1 and Ra2, and/or Ar1 and Ar2, it can be advantageous to use any as-synthesized mixtures of symmetrical and asymmetrical quinophthalones.
Preference is likewise given to compounds of the formula (I) which conform to the formula (III) or tautomeric forms thereof 
where
Z1 and Z2 are independently optionally substituted ortho-phenylene, ortho-naphthylene, peri-(1,8)-naphthylene or arylene composed of more than two fused-together benzene rings, the aryl radicals which have more than two fused-together benzene rings being bridged ortho or in a manner corresponding to a peri position in naphthalene,
and
Ar1, Ar2 and B are each as defined above.
Possible substituents for the radicals Z1 and Z2 include for example the substituents mentioned for the radical Z.
Particularly preferred radicals Z1 and Z2 independently correspond to an optionally substituted peri-(1,8)-naphthylene.
Particular preference is given to compounds of the formula (III), which conform to the formula (IIIa) 
where
n1 and m1 are independently from 0 to 4,
R5 and R6 are each independently the same or different and can be the substituents mentioned for the radicals Z1 and Z2, especially halogen or C1-C6-alkyl,
o and p are independently from 0 to 2, especially 0 or 1,
R3 and R4 are each independently the same or different and can be the substituents mentioned for the radicals Z1 and Z2, especially halogen, NO2, xe2x80x94NH-acyl or xe2x80x94NH-alkyl, and
B is as defined above. The preferred meaning of B corresponds to that indicated above.
Very particular preference is given to compounds of the formula (III)
wherein
Z1=Z2 and
Ar1=Ar2.
Of corresponding advantage are compounds of the formula (IIIa)
wherein
n1=m1,
R5=R6,
o=p and
R3=R4,
where in particular
n1, m1, o and p are each 0.
Particular preference is given to compounds of the formula (III) which conform to the formula (IIIb) or (IIIc) 
where
n1, m1, R5, R6 and B are each as defined above.
The compounds of the formula (III) according to the invention are likewise notable for excellent sublimation fastness in the mass coloration of plastics. They also possess very good light fastness, very good thermal stability and a particularly high color strength.
When the perinones of the formula (III) according to the invention have different meanings for Z1 and Z2 and/or for Ar1 and Ar2, it can be advantageous to use any as-synthesized mixtures of symmetrical and asymmetrical perinones of the formula (III).
Preference is likewise given to compounds of the formula (I) which conform to the formula (IV) or tautomeric forms thereof 
where
Y, Z, Ra, Rb, Ar1, Ar2 and B are each as defined above.
Particular preference is given to compounds of the formula (IV) which conform to the formula (IVa) or tautomeric forms thereof 
where
R1, R3, R4, R5, Rb1, Ra1, B, n, p and n1 are each as defined above.
Very particular preference is given to compounds of the formula (IV) which conform to the formula (IVb) or tautomeric forms thereof 
where
R1, R5, Rb1, B, n and n1 are each as defined above.
The compounds of the formula (IV) according to the invention are likewise notable for excellent sublimation fastness in the mass coloration of plastics. They also possess very good light fastness, good thermal stability and a particularly high colour strength.
Thermal stability is very good at temperatures as high as 300xc2x0 C. and distinctly higher.
Particular preference is given to as-synthesized mixtures containing compounds of the formula (IV) and those of the formulae (II) and (III). Of advantage are in particular those mixtures which as well as the compound of the formula (IV) contain 0 to 25% by weight of a compound of the formula (II) and 0 to 25% by weight of a compound of the formula (III), the sum total of the compounds (IV), (II) and (III) being 100%.
Compounds of the formula (V) are described for example in Plaste und Kautschuk, Volume 28, No. 11/1981, p. 601-606.
The invention further provides a process for preparing the compounds of the formula (I) according to the invention, characterized in that tetracarboxylic acids or anhydrides of the formula (V) 
where
Ar1, Ar2 and B are each as defined above,
are condensed with one or more compounds of the formulae (VI) and/or (VII) 
where
Rc is H, COOH or halogen, especially F, Br and Cl, especially H or COOH, and
Y, Z and Ra are each as defined above,
the sum total of the compounds of the formulae (VI) and (VII) being equal to two mole equivalents, based on tetracarboxylic acid (V).
The stated mole equivalents of the reactants employed for preparing the compound (I) merely serve to indicate the stoichiometry and do not preclude larger or smaller amounts which may be industrially more appropriate.
It will be appreciated that the employed compounds of the formulae (VI) and (VII) can also total more than two mole equivalents, based on tetracarboxylic acid (IV) or anhydrides thereof. However, it is preferable to use stoichiometric amounts.
The condensation reaction can be carried out directly by melting together equimolar amounts of the components of the formulae (V) and (VI) or (VII) at a temperature of 120xc2x0 C. to 250xc2x0 C. or more advantageously by reaction in a solvent at a temperature of 110xc2x0 C. to 220xc2x0 C., if appropriate under pressure, it being possible for the water of reaction to be removed by distillation.
Suitable solvents include for example: chlorobenzene, o-dichlorobenzene, trichlorobenzene, xylene, dimethylformamide, N-methylpyrrolidone glacial acetic acid, propionic acid, phenol, cresols, phenoxyethanol, glycols and mono- and dialkyl ethers thereof, alcohols, e.g., methanol, ethanol, i-propanol, n-butanol and water.
If appropriate, the reaction can be carried out in the presence of an acidic catalyst such as, for example: zinc chloride, p-toluenesulphonic acid, hydrochloric acid, sulphuric acid, organic acids, etc.
Particular preference is given to using the tetracarboxylic acid of the formula (V) in the form of its anhydride.
Preference is given to using in the process according to the invention compounds of the formula (V) which conform to the formula (Va) or anhydrides thereof 
where
R3, R4, B, o and p are each as defined above.
Very particular preference is given to using compounds of the formula (V) which conform to the formula (Vb) or the formula (Vc) or respective anhydrides thereof 
where
B is as defined above.
Preferred compounds of the formula (VI) are quinaldines of the formula (VIa) 
where
R1, Rc, Ra and n are each as defined above.
Suitable quinaldines of the formula (VIa) are for example those of the hereinbelow mentioned formulae: 
The diamines of the formula (VII) are known or can be prepared for example similarly to known diamines.
Preferred aromatic diamines of the formula (VII) are:
o-phenylenediamine, chloro-o-phenylenediamines, dichloro-o-phenylenediamines, methyl-o-phenylenediamines, ethyl-o-phenylenediamines, methoxy-o-phenylenediamines, acetamino-o-phenylenediamines, phenyl-o-phenylenediamines, naphthylene-o-diamines, also 1,8-naphthylenediamine, chloro-1,8-naphthylenediamines, dichloro-1,8-naphthylenediamines, methyl-1,8-naphthylenediamines, dimethyl-1,8-naphthylenediamines, methoxy-1,8-naphthylenediamines, ethoxy-1,8-naphthylenediamines, acetamino-1,8-naphthylenediamines and 1,8-diaminoacetnaphthylene.
In a further preferred process variant, the compound of the formula (VII) is an optionally substituted peri-naphthylenediamine, especially 1,8-naphthylenediamine.
Preference is given to the novel process for preparing compounds of the formula (I) which conform to the formula (II), this process being characterized in that tetracarboxylic acids or anhydrides of the formula (V) are condensed with compounds of the formulae (VIb) and/or (VIc) 
where
Rc1 and Rc2 are independently H, COOH or halogen, especially F, Br or Cl, especially H or COOH, and
Ra1, Ra2, Y1 and Y2 are each as defined above,
the sum total of the compounds (VIb) and (VIc) being two mole equivalents, based on tetracarboxylic acid (V).
The condensation reaction can be carried out directly by melting together equimolar amounts of the components of the formulae (V) and (VIb) or (VIc) at a temperature of 160xc2x0 C. to 250xc2x0 C., preferably 180xc2x0 C. to 220xc2x0 C., more preferably 190 to 200xc2x0 C., or more advantageously by reaction in a solvent at a temperature of 110xc2x0 C. to 220xc2x0 C. and preferably 160 to 180xc2x0 C., if appropriate under pressure, it being possible for the water of reaction to be removed by distillation.
Preferred compounds of the formula (VIb) or (VIc) are quinaldines of the formula (VIbb) 
or of the formula (VIcc) 
where
R1, R2, Rc1, Rc2, Ra1, Ra2, n and m are each as defined above.
A reaction batch for preparing the compounds of the formula (II) is preferably worked up by dilution with alcohols such as methanol, ethanol, propanol or butanol. It is similarly possible to use aromatic diluents such as chlorobenzene or toluene and also ligroin. This process according to the invention preferably gives the compound according to the invention in yields of 85 to 95% of theory.
If appropriate, the condensation reaction can be followed by a halogenation reaction, especially a chlorination or bromination reaction, in which case this halogenation reaction is carried out under conditions known per se. For instance, the bromination of compounds of the formula (II) where Rb1=Rb2=H in glacial acetic acid at a temperature of 80 to 120xc2x0 C. leads to compounds of the formula (II), where Rb1 and Rb2 are each bromine.
The process according to the invention is likewise preferable for preparing the compounds of the formula (I) which conform to the formula (III), and it is characterized in that tetracarboxylic acids or anhydrides of the formula (V) are condensed with compounds of the formulae (VIIa) and/or (VIIb) 
the sum total of the diamines (VIIa) and (VIIb) used being two mole equivalents, based on tetracarboxylic acids (V), Z1 and Z2 each being as defined above.
The condensation reaction to prepare compounds of the formula (III) can be carried out directly by melting together equimolar amounts of the components of the formulae (V) and (VIIa) or (VIIb) at a temperature of 120xc2x0 C. to 250xc2x0 C., preferably at 120 to 180xc2x0 C., or more advantageously by reaction in a solvent at a temperature of 80xc2x0 C. to 220xc2x0 C., preferably at 120 to 180xc2x0 C., if appropriate under pressure, it being possible for the water of reaction to be removed by distillation.
Compounds of the formula (III) which optionally bear substituents from the group of the alkylaminosulphonyl and arylaminosulphonyl radicals are preparable for example from the corresponding compounds of the formula (III) in which one substituent is a chlorosulphonyl radical, using alkyl- or arylamines respectively.
Compounds of the formula (III) according to the invention in which one substituent is an aryloxysulphonyl radical can also be obtained by reaction of the corresponding chlorosulphonyl dyes with phenols or naphthols in the presence of a base, for example pyridine, triethylamine, alkali or alkaline earth metal carbonates, hydroxides or oxides.
Compounds of the formula (III) in which there are substituents representing alkyloxy or acyloxy can additionally be prepared by alkylation and acylation respectively of the compounds according to the invention which bear a hydroxyl group.
Those compounds of the formula (III) having an optionally acylated or alkylated amino group are also obtainable by reduction of the corresponding compounds in which the corresponding substituent is a nitro group using customary reducing agents, for example iron, zinc, sodium sulphide, hydrogen, etc, and if appropriate subsequent acylation or alkylation. The acylating step can also be carried out in the course of the reduction by adding an acylating agent.
The reaction batch for preparing compounds of the formula (III) is preferably worked up by dilution with alcohols such as methanol, ethanol, propanol or butanol. Similarly, aromatic diluents such as chlorobenzene or toluene and also ligroin can be used. The process according to the invention preferably gives the compounds according to the invention in yields of 90 to 95% of theory.
The process according to the invention is likewise preferable for preparing compounds of the formula (I) which conform to the formula (IV), the process being characterized in that tetracarboxylic acids or anhydrides of the formula (V) are condensed with compounds of the formula (VI) and diamines of the formula (VII), the substituents on the compounds mentioned having the above-mentioned meanings and the sum total of the compounds of the formulae (VI) and (VII) being two mole equivalents, based on tetracarboxylic acid (V). Preferred compounds of the formulae (V) to (VII) are those mentioned above.
The ratio of the compounds (VI) and (VII) to each other can vary within wide limits. It is for example (VI) to (VII)=10:90 to 90:10. The ratio is preferably about 1:1.
The condensation reaction can be carried out directly by melting together equimolar amounts of the components of the formulae (V) and (VI) and (VII) at a temperature of 160xc2x0 C. to 250xc2x0 C., preferably 180 to 220xc2x0 C. and particularly preferably 190 to 200xc2x0 C. or more advantageously in a solvent at a temperature of 110xc2x0 C. to 220xc2x0 C. and preferably 160 to 180xc2x0 C., if appropriate under pressure, it being possible for the water of reaction to be removed by distillation.
The compounds of the formula (I) according to the invention are highly suitable for the mass coloration of plastics.
The term mass coloration as used herein comprehends in particular processes in which the dye is incorporated into the molten plastic material, for example with the aid of an extruder, or in which the dye is added to starting components for preparing the plastics, for example to monomers before the polymerization.
Particularly preferred plastics are thermoplastics, for example vinyl polymers, polyesters and polyamides.
Suitable vinyl polymers are polystyrene, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, styrene-butadiene-acrylonitrile terpolymers, polymethacrylate, polyvinyl chloride, etc.
Polyesters which are further suitable are polyethylene terephthalates, polycarbonates and cellulose esters.
Preference is given to polystyrene, styrene interpolymers, polycarbonates and polymethacrylate. Particular preference is given to polystyrene.
The high molecular weight compounds mentioned can be present individually or in mixtures, as plastically deformable compositions or melts.
The dyes, according to the invention, are used in finely divided form, for which the use of dispersants is possible but not mandatory.
When the compounds (I) are used after polymerization, they are preferably mixed or ground dry with the polymer chips and this mixture is plastificated and homogenized, for example on mixing rolls or in screws, but the dyes can also be added to the liquid melt and homogeneously dispersed therein by stirring. The thus precolored material is then further processed as usual, for example by spinning, into bristles, filaments, etc or by extrusion or injection moulding into shaped articles.
Since the dyes of the formula (I) are stable to polymerization catalysts, especially peroxides, it is also possible to add the dyes to the monomeric starting materials for the plastics and then to polymerize in the presence of polymerization catalysts. To this end, the dyes are preferably dissolved in or intimately mixed with the monomeric components.
The dyes of the formula (I) according to the invention are particularly readily soluble in monomeric starting materials for plastics (e.g., methyl methacrylate).
The dyes of the formula (I) are preferably used for colouring the polymers mentioned in amounts from 0.0001 to 1% by weight and especially 0.01 to 0.5% by weight, based on the amount of polymer.
By adding pigments insoluble in the polymers, for example titanium dioxide, it is possible to obtain corresponding valuable hiding colorations.
Titanium dioxide can be used in an amount of 0.01 to 10% by weight and preferably 0.1 to 5% by weight, based on the amount of polymer.
The process according to the invention can also utilize mixtures of various dyes of the formula (I) and/or mixtures of dyes of the formula (I) with other dyes and/or inorganic or organic pigments.
The compounds of the formula (II) are yellow, and the compounds of the formula (III) and those of the formula (V) are orange.
The examples hereinbelow, in which parts and percentages are by weight, illustrate the invention.